CN112368305B - Curable composition for flexible coating - Google Patents
Curable composition for flexible coating Download PDFInfo
- Publication number
- CN112368305B CN112368305B CN201980045049.XA CN201980045049A CN112368305B CN 112368305 B CN112368305 B CN 112368305B CN 201980045049 A CN201980045049 A CN 201980045049A CN 112368305 B CN112368305 B CN 112368305B
- Authority
- CN
- China
- Prior art keywords
- group
- oxyethylene
- perfluoropolyether
- curable composition
- active energy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 238000000576 coating method Methods 0.000 title claims abstract description 52
- 239000011248 coating agent Substances 0.000 title claims abstract description 48
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 59
- 125000006353 oxyethylene group Chemical group 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims abstract 5
- 239000011247 coating layer Substances 0.000 claims abstract 2
- -1 acrylate compound Chemical class 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 23
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 19
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 13
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 12
- 230000001678 irradiating effect Effects 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims 1
- 238000005299 abrasion Methods 0.000 abstract description 14
- 229920000728 polyester Polymers 0.000 description 22
- 238000012360 testing method Methods 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 18
- 239000003607 modifier Substances 0.000 description 16
- 238000005452 bending Methods 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- 230000003373 anti-fouling effect Effects 0.000 description 10
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 125000006356 alkylene carbonyl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical group FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- QASBHTCRFDZQAM-UHFFFAOYSA-N (2-isocyanato-2-methyl-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(C)(COC(=O)C=C)N=C=O QASBHTCRFDZQAM-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- AGNTUZCMJBTHOG-UHFFFAOYSA-N 3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]propane-1,2-diol Chemical compound OCC(O)COCC(O)COCC(O)CO AGNTUZCMJBTHOG-UHFFFAOYSA-N 0.000 description 1
- WOKDXPHSIQRTJF-UHFFFAOYSA-N 3-[3-[3-[3-[3-[3-[3-[3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]-2-hydroxypropoxy]propane-1,2-diol Chemical class OCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)COCC(O)CO WOKDXPHSIQRTJF-UHFFFAOYSA-N 0.000 description 1
- NTKBNCABAMQDIG-UHFFFAOYSA-N 3-butoxypropan-1-ol Chemical compound CCCCOCCCO NTKBNCABAMQDIG-UHFFFAOYSA-N 0.000 description 1
- GBSGXZBOFKJGMG-UHFFFAOYSA-N 3-propan-2-yloxypropan-1-ol Chemical compound CC(C)OCCCO GBSGXZBOFKJGMG-UHFFFAOYSA-N 0.000 description 1
- IXAUCVOJRVFRBJ-UHFFFAOYSA-N 4-(trichloromethyl)triazine Chemical class ClC(Cl)(Cl)C1=CC=NN=N1 IXAUCVOJRVFRBJ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 description 1
- NNVDGGDSRRQJMV-UHFFFAOYSA-L [dioctyl(2,2,5,5-tetramethylhexanoyloxy)stannyl] 2,2,5,5-tetramethylhexanoate Chemical compound CCCCCCCC[Sn](OC(=O)C(C)(C)CCC(C)(C)C)(OC(=O)C(C)(C)CCC(C)(C)C)CCCCCCCC NNVDGGDSRRQJMV-UHFFFAOYSA-L 0.000 description 1
- IPTNXMGXEGQYSY-UHFFFAOYSA-N acetic acid;1-methoxybutan-1-ol Chemical compound CC(O)=O.CCCC(O)OC IPTNXMGXEGQYSY-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Polymerisation Methods In General (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Polyethers (AREA)
Abstract
The invention provides a curable composition capable of forming a hard coat layer having extremely high scratch resistance and stretchability and having abrasion resistance. The solution is a curable composition and a hard coating film with a hard coating layer formed by the composition, wherein the curable composition comprises: 100 parts by mass of (a) an oxyethylene-modified polyfunctional monomer having at least 3 active energy ray-polymerizable groups and an average oxyethylene modification amount of less than 3 moles per 1 mole of the polymerizable group, (b) 0.1 to 10 parts by mass of a perfluoropolyether having an active energy ray-polymerizable group via a urethane bond at both ends of a molecular chain containing a poly (oxyperfluoroalkylene group), and (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, the perfluoropolyether being excluded from the perfluoropolyethers having a poly (oxyperfluoroalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond.
Description
Technical Field
The present invention relates to a curable composition useful as a hard coat layer forming material suitable for the surface of a flexible display or the like. More specifically, the present invention relates to a curable composition capable of forming a hard coat layer having extremely high scratch resistance, flex resistance and stretchability, and also having abrasion resistance.
Background
Mobile phones are widely used as indispensable products in our lives. In recent years, as a display of a mobile phone or the like, a bendable display, a so-called flexible display, has been developed. Flexible displays are capable of deformation such as bending and winding, and are expected to be widely used as portable displays.
In general, cover glass is used on the surface of a mobile phone to prevent damage to a display. However, glass is generally hard to bend and return, and therefore cannot be applied to a flexible display. Therefore, it has been attempted to use a plastic film having a hard coat layer having scratch resistance. In these plastic films provided with a hard coat layer, when the hard coat layer is provided on the outer side and bent, stress in the tensile direction is generated in the hard coat layer. Therefore, the hard coat layer is required to have a certain stretchability.
In order to impart scratch resistance to a hard coat layer, for example, a method of forming a highly crosslinked structure, that is, a crosslinked structure having low molecular mobility to improve surface hardness and impart resistance to external force is generally employed. As these hard coat layer forming materials, multifunctional acrylate-based materials three-dimensionally crosslinked by radicals are most used at present. However, the multifunctional acrylate-based material generally does not have stretchability because of its high crosslinking density. Therefore, there is a trade-off between the stretchability and the scratch resistance of the hard coat layer, and it is called a problem to combine these two properties.
As a method for achieving both the stretchability and the scratch resistance of the hard coat layer, a technique of using a multifunctional urethane acrylate oligomer in combination with a multifunctional acrylate modified with an oxyethylene group having high molecular mobility has been disclosed (patent document 1).
Among them, the flexible display is mounted with a touch panel, and is operated by touching the touch panel with a finger. Therefore, a fingerprint is attached to the touch panel every time a finger touches the touch panel, and the appearance of the touch panel is impaired. In order to prevent moisture and oil from adhering to the fingerprint, it is strongly desired to impart water repellency and oil repellency to the hard coat layer. From such a viewpoint, the surface of the hard coat layer is desired to have antifouling property against fingerprints and the like. However, even if the antifouling property of the hard coat layer reaches a high level at the initial stage of use, the function of antifouling property is lowered in most cases in use because a person touches it with hands every day. Therefore, there is a problem in durability of antifouling property during use.
In general, as a method for imparting antifouling property to the surface of the hard coat layer, a method of adding a small amount of a fluorine-based surface modifier to a coating liquid for forming the hard coat layer is employed. The added fluorine-based surface modifier segregates on the surface of the hard coat layer due to its low surface energy, thereby imparting water repellency and oil repellency. As the fluorine-based surface modifier, an oligomer having a poly (oxyperfluoroalkylene) chain, called perfluoropolyether, having a number average molecular weight of about 1,000 to 5,000 is used from the viewpoint of water repellency and oil repellency. However, the perfluoropolyether is generally difficult to dissolve in an organic solvent used in a coating liquid for forming a hard coat layer because of its high fluorine concentration. In addition, aggregation in the formed hard coat layer may be caused.
In order to impart solubility in organic solvents and dispersibility in hard coatings to such perfluoropolyethers, a method of introducing organic sites into the perfluoropolyethers is employed. In addition, in order to impart scratch resistance, a method of bonding an active energy ray-curable site typified by a (meth) acrylate group is used.
Heretofore, as an antifouling hard coat layer having scratch resistance, a technique has been disclosed in which a compound having a (meth) acryloyl group at both ends of a poly (oxyperfluoroalkylene) chain via a poly (oxyalkylene) group and one urethane bond is used as a surface modifier (patent document 2).
Documents of the prior art
Patent document
Patent document 1 International publication No. 2013/191254
Patent document 2 International publication No. 2016/163479
Disclosure of Invention
Problems to be solved by the invention
However, the method described in patent document 1 has a problem in terms of stretchability because a polyfunctional urethane acrylate is blended in order to impart scratch resistance. In addition, the surface modifier described in patent document 2 has a problem in terms of its antifouling property.
That is, an object of the present invention is to provide a curable composition capable of forming a hard coat layer having extremely high scratch resistance, bending resistance and stretchability and also having abrasion resistance.
Means for solving the problems
The present inventors have made extensive studies to achieve the above object and as a result, have found that a curable composition comprising a perfluoropolyether having an active energy ray-polymerizable group via a urethane bond without via a poly (oxyalkylene) group at both ends of a molecular chain containing a poly (oxyperfluoroalkylene group) and an oxyethylene-modified polyfunctional monomer having at least 3 active energy ray-polymerizable groups, wherein the average oxyethylene modification amount of the oxyethylene-modified polyfunctional monomer is less than 3mol based on 1mol of the polymerizable group, can form a hard coat layer having extremely high abrasion resistance, bending resistance and stretchability and also having abrasion resistance, thereby completing the present invention.
Namely, the 1 st aspect of the present invention relates to a curable composition comprising: 100 parts by mass of (a) an oxyethylene-modified polyfunctional monomer, (b) 0.1 to 10 parts by mass of a perfluoropolyether, and (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays,
the oxyethylene-modified polyfunctional monomer (a) has at least 3 active energy ray-polymerizable groups and has an average oxyethylene modification amount of less than 3mol per 1mol of the polymerizable groups,
the perfluoropolyether (b) is a perfluoropolyether having an active energy ray-polymerizable group via a urethane bond at both ends of a molecular chain containing a poly (oxyperfluoroalkylene group), but the perfluoropolyether does not include a perfluoropolyether having a poly (oxyperfluoroalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond.
The 2 nd aspect relates to the curable composition according to the 1 st aspect, wherein the perfluoropolyether (b) has at least 2 active energy ray-polymerizable groups at each end.
The aspect 3 relates to the curable composition according to the aspect 2, wherein the perfluoropolyether (b) has at least 3 active energy ray-polymerizable groups at each end.
The 4 th aspect of the present invention is the curable composition according to any one of the 1 st to 3 th aspects, wherein the poly (oxyperfluoroalkylene) group has- [ OCF ] 2 ]-and- [ OCF 2 CF 2 ]-a radical as repeating unit.
The aspect 5 relates to the curable composition according to the aspect 4, wherein the perfluoropolyether (b) has a structural moiety represented by the following formula [1 ].
(formula [1]]Wherein n represents a repeating unit- [ OCF ] 2 CF 2 ]The number and repeating units of- [ OCF ] 2 ]-total number of numbers. )
Viewpoint 6 relates to the curable composition according to any one of viewpoints 1 to 5, wherein the oxyethylene modified polyfunctional monomer (a) contains at least 1 compound selected from the group consisting of an oxyethylene modified polyfunctional (meth) acrylate compound and an oxyethylene modified polyfunctional urethane (meth) acrylate compound.
An aspect 7 relates to the curable composition of any one of aspects 1 to 6, wherein the average oxyethylene modified amount of the oxyethylene modified polyfunctional monomer (a) is 2mol or less based on 1mol of the polymerizable group.
The 8 th aspect relates to the curable composition according to any one of the 1 st to 7 th aspects, which further comprises (d) a solvent.
The 9 th aspect relates to a cured film obtained from the curable composition according to any one of the 1 st to 8 th aspects.
The 10 th aspect relates to a hard coat film comprising a hard coat layer on at least one surface of a film base, wherein the hard coat layer is the cured film according to the 9 th aspect.
An 11 th aspect relates to a hard coat film having a hard coat layer on at least one surface of a film base material, the hard coat layer being formed by a method comprising: a step of forming a coating film by applying the curable composition according to any one of aspects 1 to 8 on a film base, and a step of curing the coating film by irradiating the coating film with an active energy ray.
The hard coat film according to claim 12, wherein the hard coat layer has a film thickness of 1 to 10 μm.
The 13 th aspect relates to a method for producing a laminate, comprising: a step of forming a coating film by applying the curable composition according to any one of aspects 1 to 8 to a film base, and a step of curing the coating film by irradiating the coating film with an active energy ray.
Effects of the invention
According to the present invention, a curable composition capable of forming a hard coat layer having extremely high scratch resistance, bending resistance and stretchability and also having wear resistance can be provided.
Detailed description of the invention
< curable composition >
The curable composition of the present invention is specifically a curable composition comprising: 100 parts by mass of (a) an oxyethylene-modified polyfunctional monomer, (b) 0.1 to 10 parts by mass of a perfluoropolyether, and (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays,
the oxyethylene-modified polyfunctional monomer (a) has at least 3 active energy ray-polymerizable groups and has an average oxyethylene modification amount of less than 3mol per 1mol of the polymerizable groups,
the perfluoropolyether (b) is a perfluoropolyether having an active energy ray-polymerizable group via a urethane bond at both ends of a molecular chain containing a poly (oxyperfluoroalkylene group), but the perfluoropolyether does not include a perfluoropolyether having a poly (oxyperfluoroalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond.
The following first describes the respective components (a) to (c) described above.
[ (a) an oxyethylene-modified polyfunctional monomer having at least 3 active energy ray-polymerizable groups and an average oxyethylene modification amount of less than 3mol per 1mol of the polymerizable groups (also referred to simply as (a) an oxyethylene-modified polyfunctional monomer having at least 3 active energy ray-polymerizable groups) ]
An oxyethylene-modified polyfunctional monomer having at least 3 active energy ray-polymerizable groups, which has at least 3 active energy ray-polymerizable groups, and the average oxyethylene modification amount is less than 3mol based on 1mol of the polymerizable groups.
The preferred oxyethylene modified polyfunctional monomer (a) having at least 3 active energy ray-polymerizable groups in the curable composition of the present invention is a monomer selected from the group consisting of an oxyethylene modified polyfunctional (meth) acrylate compound and an oxyethylene modified polyfunctional urethane (meth) acrylate compound, which has at least 3 active energy ray-polymerizable groups and an average oxyethylene modified amount of less than 3mol per 1mol of the polymerizable groups.
In the present invention, the (meth) acrylate compound means both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.
(a) The average oxyethylene modification amount in the oxyethylene-modified polyfunctional monomer having at least 3 active energy ray-polymerizable groups is less than 3mol of active energy ray-polymerizable groups per 1mol of the monomer, and preferably 2mol or less of active energy ray-polymerizable groups per 1mol of the monomer.
In addition, (a) the average oxyethylene modification amount in the oxyethylene-modified polyfunctional monomer having at least 3 active energy ray-polymerizable groups is preferably 0.1mol or more, more preferably 0.5mol or more based on 1mol of the active energy ray-polymerizable group contained in the monomer, and more preferably more than 0mol based on 1mol of the active energy ray-polymerizable group contained in the monomer.
Examples of the oxyethylene-modified polyfunctional (meth) acrylate compound include (meth) acrylate compounds of oxyethylene-modified polyols.
Examples of the polyhydric alcohol include glycerin, diglycerin, triglycerol, tetraglycerin, pentaglycerin, hexaglycerin, decaglycerin, polyglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.
Examples of the active energy ray-polymerizable group in the (a) oxyethylene group-modified polyfunctional monomer having at least 3 active energy ray-polymerizable groups include a (meth) acryloyl group, a vinyl group and an epoxy group.
The addition number of oxyethylene groups of the oxyethylene group-modified polyfunctional monomer having at least 3 active energy ray-polymerizable groups per 1 molecule (a) is 1 to 30, preferably 1 to 12.
In the present invention, the above-mentioned (a) oxyethylene group-modified polyfunctional monomer having at least 3 active energy ray-polymerizable groups may be used alone, or two or more kinds may be used in combination.
[ (b) perfluoropolyether having active energy ray-polymerizable groups via urethane bonds at both ends of a molecular chain containing poly (oxyperfluoroalkylene) (excluding perfluoropolyether having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond) ]
In the present invention, as the component (b), a perfluoropolyether having an active energy ray-polymerizable group not via a poly (oxyalkylene) group but via a urethane bond at both terminals of a molecular chain containing a poly (oxyperfluoroalkylene) (hereinafter, also simply referred to as "perfluoropolyether having a polymerizable group at both terminals" (b) ") is used. (b) The component (B) functions as a surface modifier in a hard coat layer to which the curable composition of the present invention is applied.
Further, the hard coat layer exhibiting a transparent appearance can be formed by suppressing the occurrence of white turbidity in the hard coat layer by virtue of excellent compatibility between the component (b) and the component (a).
The poly (oxyalkylene) group is a group in which the number of oxyalkylene repeating units is 2 or more and an alkylene group in the oxyalkylene group is an unsubstituted alkylene group.
The number of carbon atoms of the alkylene group in the poly (oxyperfluoroalkylene) group is not particularly limited, and it is preferably 1 to 4. That is, the poly (oxyperfluoroalkylene) group means a group having a structure in which a 2-valent carbon fluoride group having 1 to 4 carbon atoms and an oxygen atom are alternately bonded, and the oxyperfluoroalkylene group means a group having a structure in which a 2-valent carbon fluoride group having 1 to 4 carbon atoms and an oxygen atom are bonded. Specifically, there may be mentioned- [ OCF ] 2 ]- (oxyperfluoromethylene), - [ OCF 2 CF 2 ]- (oxyperfluoroethylene), - [ OCF 2 CF 2 CF 2 ]- (oxyperfluoropropane-1,3-diyl), [ OCF 2 C(CF 3 )F]- (oxyperfluoropropane-1,2-diyl), and the like.
The above-mentioned oxyperfluoroalkylene group may be used singly or in combination of two or more, and in this case, the bonding of plural oxyperfluoroalkylene groups may be either block bonding or random bonding.
Among them, it is preferable to use a poly (oxyperfluoroalkylene) group having- [ OCF ] from the viewpoint of obtaining a cured film having good abrasion resistance 2 ]- (oxyperfluoromethylene) and- [ OCF 2 CF 2 ]Both (oxyperfluoroethylene) as the group of the repeating unit.
Among them, the poly (oxyperfluoroalkylene) group is preferably [ repeating unit- [ OCF ] 2 ]-]: [ repeating Unit- [ OCF 2 CF 2 ]-]=2:1 to 1:2 contains a repeating unit- [ OCF ] 2 ]-and- [ OCF 2 CF 2 ]-more preferably in a molar ratio of about 1:1 contains a repeating unit- [ OCF ] 2 ]-and- [ OCF 2 CF 2 ]-a group of (a). The bonding of these repeating units may be either block bonding or random bonding.
The number of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, more preferably 7 to 21, in terms of the total number of the repeating units.
The poly (oxyperfluoroalkylene) group has a weight average molecular weight (Mw) of 1,000 to 5,000, preferably 1,500 to 3,000 or 1,500 to 2,000, as measured in terms of polystyrene by Gel Permeation Chromatography (GPC).
Examples of the active energy ray-polymerizable group bonded via a urethane bond include a (meth) acryloyl group and a vinyl group.
(b) The perfluoropolyether having polymerizable groups at both ends is not limited to those having 1 active energy ray-polymerizable group such as a (meth) acryloyl group at each end, and may be those having 2 or more active energy ray-polymerizable groups at both ends, and examples of the terminal structure containing an active energy ray-polymerizable group include the following structures [ A1] to [ A5] and structures in which acryloyl groups are replaced with methacryloyl groups.
As the perfluoropolyether having polymerizable groups at both ends (b), for example, perfluoropolyethers having at least 2 active energy ray-polymerizable groups at both ends, respectively, and perfluoropolyethers having at least 3 active energy ray-polymerizable groups at both ends, respectively, are preferable.
Examples of the perfluoropolyether having a polymerizable group at both ends of the (b) include compounds represented by the following formula [2 ].
(wherein A represents the formula [ A1]]-formula [ A5]1 of the structures shown and structures in which acryloyl groups in these structures are replaced with methacryloyl groups, PFPE represents the poly (oxyperfluoroalkylene) groupGroup (wherein with L) 1 One side of the bond is an oxygen terminal, with L 2 The bonded side is a perfluoroalkylene terminus. ) L is 1 And L 2 Represents an alkylene group or an alkylenecarbonyl group having 2 or 3 carbon atoms and substituted by 1 to 3 fluorine atoms, n independently represents an integer of 1 to 5, L 3 Represents an n + 1-valent residue obtained by removing OH from an n + 1-valent alcohol. )
Examples of the above alkylene group or alkylenecarbonyl group having 2 or 3 carbon atoms and substituted by 1 to 3 fluorine atoms include-CH 2 CHF-、-CH 2 CF 2 -、-CHFCF 2 -、-CH 2 CH 2 CHF-、-CH 2 CH 2 CF 2 -、-CH 2 CHFCF 2 -、-C(＝O)CF 2 -, preferably CH 2 CF 2 。
As the above formula [2]The moiety (A-NHC (= O) in the compound represented n L 3 Examples thereof include the following formula [ B1]-formula [ B12]The structure shown.
(wherein A represents 1 of the structures represented by the formulae [ A1] to [ A5] and the structures in which an acryloyl group is replaced by a methacryloyl group.)
In the structures represented by the above formulas [ B1] to [ B12], the formulas [ B1] and [ B2] correspond to n =1, the formulas [ B3] to [ B6] correspond to n =2, the formulas [ B7] to [ B9] correspond to n =3, and the formulas [ B10] to [ B12] correspond to n = 5.
Among them, the structure represented by the formula [ B3] is preferable, and the combination of the formula [ B3] and the formula [ A3] is particularly preferable.
Preferable examples of (b) the perfluoropolyether having a polymerizable group at both ends include compounds having a structural moiety represented by the following formula [1 ].
The moiety represented by the above formula [1] corresponds to a moiety of the compound represented by the above formula [2] excluding a-NHC (= O) -.
The formula [1]In (a) n represents a repeating unit- [ OCF ] 2 CF 2 ]The number and repeating units of- [ OCF ] 2 ]The total number of-units is preferably in the range of 5 to 30, more preferably in the range of 7 to 21. In addition, the repeating unit- [ OCF ] 2 CF 2 ]The number and repeating units of- [ OCF ] 2 ]The ratio of the quantities of-is preferably 2:1 to 1:2, more preferably about 1:1, in the above range. The bonding of these repeating units may be either block bonding or random bonding.
In the present invention, the perfluoropolyether (b) having polymerizable groups at both ends is used in an amount of 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass, based on 100 parts by mass of the (a) oxyethylene modified polyfunctional monomer having at least 3 active energy ray polymerizable groups.
The perfluoropolyether having polymerizable groups at both ends of the above-mentioned (b) can be prepared, for example, by the following formula [3]
(HO) n L 3 -O-L 1 -PFPE-O-L 2 -O-L 3 (OH) n [3]
(wherein PFPE, L 1 、L 2 、L 3 And n represents the same meaning as described above. ) The hydroxyl groups present at both ends of the compound represented by the formula [ A1], are reacted with an isocyanate compound having a polymerizable group]-formula [ A5]The structures shown in the above and compounds in which an acryloyl group in these structures is replaced with a methacryloyl group and an isocyanate group is bonded to a bonding site (for example, 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate) are reacted to form a urethane bond.
In addition, the curable composition of the present invention may contain, in addition to (b) perfluoropolyether having active energy ray-polymerizable groups via urethane bonds at both ends of a molecular chain containing poly (oxyperfluoroalkylene) (however, no poly (oxyalkylene) group is present between the poly (oxyperfluoroalkylene) group and the urethane bond), perfluoropolyether having an active energy ray-polymerizable group via a urethane bond at one end of a molecular chain containing poly (oxyperfluoroalkylene) (however, no poly (oxyalkylene) group is present between the poly (oxyperfluoroalkylene) group and the hydroxyl group at the other end of the molecular chain) (also, those represented by the above formula [3], perfluoropolyethers having hydroxyl groups at both ends of a molecular chain containing poly (oxyperfluoroalkylene) (but no poly (oxyperfluoroalkylene) group is present between the poly (oxyperfluoroalkylene) group and the hydroxyl group) [ compounds having no active energy ray-polymerizable groups ].
The present invention also relates to a perfluoropolyether compound having at least 3 active energy ray-polymerizable groups via urethane bonds at both ends of a molecular chain containing a poly (oxyperfluoroalkylene group) (excluding a perfluoropolyether having a poly (oxyperfluoroalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond).
The perfluoropolyether compound having polymerizable groups at both ends is preferably a compound having a moiety represented by the formula [1 ].
The perfluoropolyether compound of the present invention has excellent compatibility with the component (a) as described above, and thereby the occurrence of white turbidity in the hard coat layer is suppressed, and an excellent effect of forming a hard coat layer exhibiting a transparent appearance is achieved.
The present invention also relates to a surface modifier containing the above perfluoropolyether compound, and the use of the perfluoropolyether compound for surface modification.
[ (c) polymerization initiator generating free radical by active energy ray ]
The polymerization initiator which generates radicals by active energy rays (hereinafter also referred to simply as "polymerization initiator (c)") which is preferable in the curable composition of the present invention is, for example, a polymerization initiator which generates radicals by active energy rays such as electron beams, ultraviolet rays, and X-rays, particularly by irradiation with ultraviolet rays.
Examples of the polymerization initiator (c) include benzoins, alkylbenzophenones, thioxanthones, azos, azides, diazos, o-quinonediazines, acylphosphine oxides, oxime esters, organic peroxides, benzophenones, biscoumarins, bisimidazoles, metallocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, iodonium salts, sulfonium salts, and other onium salts. These may be used alone or in combination of two or more.
Among the polymerization initiators (c), in the present invention, alkylbenzophenones are preferably used as the polymerization initiator (c) from the viewpoint of transparency, surface curability, and film curability. By using the alkylphenones, a cured film having further improved scratch resistance can be obtained.
Examples of the alkylphenones include α -hydroxyalkylbenzones such as 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one, and 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropanoyl) benzyl) phenyl) -2-methylpropan-1-one; α -aminoalkylbenzophenones such as 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one; 2,2-dimethoxy-1,2-diphenylethan-1-one; methyl phenylglyoxylate.
In the present invention, the polymerization initiator (c) is used in a proportion of 1 to 20 parts by mass, preferably 2 to 10 parts by mass, based on 100 parts by mass of the above-mentioned (a) oxyethylene modified polyfunctional monomer having at least 3 active energy ray-polymerizable groups.
[ (d) solvent ]
The curable composition of the present invention may further contain (d) a solvent, and may be in the form of a varnish (film-forming material).
The solvent may be appropriately selected in consideration of the solubility of the components (a) to (c), the workability in coating for forming a cured film (hard coat layer) described later, and the drying property before and after curing. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetrahydronaphthalene; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral oil, cyclohexane, etc.; halides such as monochloromethane, monobromomethane, monoiodomethane, dichloromethane, trichloromethane, tetrachloromethane, trichloroethane, tetrachloroethylene, o-dichlorobenzene, and the like; esters or ester ethers such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, and propylene glycol mono-n-butyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexanol, benzyl alcohol and ethylene glycol; amides such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide, and a mixture of 2 or more of these solvents.
(d) The amount of the solvent used is not particularly limited, and the solid content concentration in the curable composition of the present invention is, for example, 1 to 70% by mass, preferably 5 to 50% by mass. The solid content concentration (also referred to as nonvolatile content concentration) represents the content of the solid content (component obtained by removing the solvent component from the total components) based on the total mass (total mass) of the components (a) to (d) (and other additives as desired) in the curable composition of the present invention.
[ other additives ]
In the curable composition of the present invention, if necessary, additives usually added, for example, a polymerization inhibitor, a photosensitizing agent, a leveling agent, a surfactant, an adhesion imparting agent, a plasticizer, an ultraviolet absorber, an antioxidant, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment, and a dye may be appropriately blended as long as the effects of the present invention are not impaired.
< cured film >
The curable composition of the present invention can be formed into a cured film by coating (applying) a coating film on a substrate and irradiating the coating film with active energy rays to polymerize (cure). The cured film is also an object of the present invention. In addition, a hard coat layer in a hard coat film described later may be formed from the cured film.
Examples of the base material in this case include various resins (e.g., polyesters such AS polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefins, polyamides, polyimides, epoxy resins, melamine resins, triacetyl cellulose, acrylonitrile-butadiene-styrene copolymers (ABS), acrylonitrile-styrene copolymers (AS), norbornene resins, thermoplastic Polyurethanes (TPU)), metals, woods, papers, glasses, and slates. The shape of these substrates may be a plate, a film or a three-dimensional molded body.
The coating method on the substrate may be appropriately selected, for example, from the group consisting of a casting coating method, a spin coating method, a knife coating method, a dip coating method, a roll coating method, a spray coating method, a bar coating method, a die coating method, an ink jet method, and a printing method (for example, a relief printing method, a gravure printing method, a planographic printing method, and a screen printing method). It is preferable that the curable composition is filtered by a filter having a pore size of about 0.2 μm and then applied. In addition, a solvent may be added to the curable composition as needed to form a paint form at the time of coating. Examples of the solvent in this case include various solvents listed above as the solvent (d).
After a curable composition is applied to a substrate to form a coating film, the coating film is pre-dried by heating means such as a hot plate or an oven as necessary to remove the solvent (solvent removal step). The conditions for the heat drying at this time are preferably about 30 seconds to 10 minutes at 40 ℃ to 120 ℃, for example.
After drying, the coating film is cured by irradiation with active energy rays such as ultraviolet rays. Examples of the active energy ray include ultraviolet rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. Examples of the light source used for ultraviolet irradiation include sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs.
Then, the polymerization can be completed by post-baking, specifically, by heating with a heating means such as a hot plate or an oven.
The thickness of the cured film formed is usually 0.01 to 50 μm, preferably 0.05 to 20 μm, after drying and curing.
< hard coating film >
A hard coat film having a hard coat layer on at least one surface (surface) of a film substrate can be produced using the curable composition of the present invention. The hard coat film is also an object of the present invention, and can be suitably used for protecting the surface of various display elements such as a flexible display.
The hard coat layer in the hard coat film of the present invention can be formed by a method comprising a step of applying the curable composition of the present invention on a film substrate to form a coating film and a step of irradiating the coating film with active energy rays such as ultraviolet rays to cure the coating film.
As the film substrate, various transparent resin films that can be used for optical applications can be used as the substrate mentioned in < cured film >. Preferable examples of the resin film include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN), polycarbonates, polymethacrylates, polystyrenes, polyolefins, polyamides, polyimides, triacetylcelluloses and Thermoplastic Polyurethanes (TPU).
In addition, a method of applying the curable composition to the film base material (coating film forming step) and a method of irradiating the coating film with active energy rays (the curing step may use the method mentioned in the above-mentioned < cured film >. The case where the curable composition of the present invention contains a solvent (in the form of a varnish), the method may further include a step of drying the coating film to remove the solvent, if necessary, after the coating film forming step.
The film thickness of the hard coat layer thus obtained is preferably 1 to 20 μm, more preferably 1 to 10 μm.
The present invention also relates to a method for producing a laminate, which comprises a step of applying the curable composition described above on a film substrate to form a coating film and a step of irradiating the coating film with active energy rays to cure the coating film.
The step of applying a coating film on the film base and the step of irradiating the coating film with active energy rays to cure the coating film can be performed under the same operation and conditions as described above.
Examples
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples.
In the examples, the apparatus and conditions used for the preparation of the patterns and the analysis of the physical properties were as follows.
(1) Coating with a bar coater
The device comprises the following steps: PM-9050MC manufactured by エスエムテー
Stick: 8978 Zxft 8978A-Bar OSP-22, maximum wet film thickness 22 μm (equivalent to wire Bar # 9)
Coating speed: 4 m/min
(2) Baking oven
The device comprises the following steps: 5363 dust-free dryer DRC433FA manufactured by アドバンテック DONGAIYANG
(3) UV curing
The device comprises the following steps: CV-110QC-G manufactured by ヘレウス
ランプ: 8978 Zxft 8978 Kabushiki Kaisha high pressure mercury lamp H-bulb
(4) Gel Permeation Chromatography (GPC)
The device comprises the following steps: HLC-8220GPC manufactured by imperial ソー (Chinese character of imperial egg, china)
Column: shodex (registered trademark) GPC K-804L and GPC K-805L manufactured by Showa Denko K.K
Column temperature: 40 deg.C
Eluent: tetrahydrofuran (THF)
A detector: RI (Ri)
(5) Scratch resistance test
The device comprises the following steps: the reciprocating abrasion tester TRIBOGEAR TYPE manufactured by Xindong science (strain): 30S
Scanning speed: 3,000mm/min
Scanning distance: 50mm
(6) Contact angle
The device comprises the following steps: dropMaster DM-501 made by cooperative interfacial science (strain)
Measuring temperature: 20 deg.C
(7) Bending test
The device comprises the following steps: 8978 Zxft 8978 cylindrical Mandelier bending tester
(8) Tensile test
The device comprises the following steps: automatic drawing AGS-10kNX of bench precision universal tester manufactured by Shimadzu corporation
A clamp: 1kN manual thread type plane clamp
A fixture tooth: high-strength rubber-coated fixture tooth
Stretching speed: 50 mm/min
Measuring temperature: 23 deg.C
(9) Abrasion resistance test
The device comprises the following steps: the reciprocating abrasion tester TRIBOGEAR TYPE manufactured by Xindong science (strain): 30S
Scanning speed: 4,500mm/min
Scanning distance: 50mm
In addition, abbreviations have the following meanings.
a-1: oxyethylene-modified trimethylolpropane triacrylate [ アロニックス (registered trademark) M-350, manufactured by Toyo Seiya Kabushiki Kaisha, 3mol of oxyethylene group ]
a-2: oxyethylene-modified pentaerythritol tetraacrylate [ KAYALAD RP-1040, oxyethylene 4mol, manufactured by Nippon Kagaku corporation ]
a-3: oxyethylene-modified diglycerol tetraacrylate [ アロニックス (registered trademark) M-460, oxyethylene 4mol, manufactured by Toyo Produce
a-4: oxyethylene-modified tetraglycerin polyacrylate [ SA-TE6, number of functional groups 6, oxyethylene group 6mol, manufactured by Saka pharmaceutical industry Co., ltd ]
a-5: oxyethylene-modified decaglycerol polyacrylate [ SA-ZE12, number of functional groups 12, oxyethylene group 12mol, manufactured by Saka pharmaceutical industry Co., ltd ]
a-6: oxyethylene-modified dipentaerythritol hexaacrylate [ KAYALAD DPEA-12 and oxyethylene group 12mol, manufactured by Nippon Kagaku Co., ltd ]
a-51: trimethylolpropane triacrylate [ NK エステル A-TMPT manufactured by Xinzhongcun chemical industry Co., ltd ]
a-52: glycerol triacrylate [ アロニックス (registered trademark) MT-3547, manufactured by Toyo Seiya Kabushiki Kaisha ]
a-53: pentaerythritol triacrylate/pentaerythritol tetraacrylate mixture KAYALAD PET-30, manufactured by Nippon Kagaku K.K.)
a-54: dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture (KAYALAD DPHA, manufactured by Nippon Kagaku Co., ltd.)
a-55: oxypropylene-modified trimethylolpropane triacrylate (アロニックス (registered trademark) M-310, 3mol of oxy (methylethylidene) group, manufactured by east Asia Co., ltd.)
a-56: oxypropylene-modified glyceryl triacrylate [ OTA480, 3mol of oxy (methylethylene) group, available from ダイセル, オルネクス Co. ]
a-57: oxyethylene modified glyceryl triacrylate [ NK エステル A-GLY-9E, oxyethylene 9mol, manufactured by Xinzhongcun chemical industry Co., ltd ]
PFPE1: perfluoropolyether having 2 hydroxyl groups at both ends thereof without interposing a poly (oxyalkylene) group [ Fomblin (registered trademark) T4 manufactured by ソルベイスペシャルティポリマーズ ]
BEI:1,1-bis (acryloyloxymethyl) ethyl isocyanate カレンズ (registered trademark) BEI manufactured by SHO AND ELECTRIC WORKING CORPORATION
AOI: 2-Acryloxyethyl isocyanate [ カレンズ (registered trademark) AOI manufactured by SHO AND ELECTRIC WORKING (KOKAI) ]
DOTDD: dioctyltin dineodecanoate [ ネオスタン (registered trademark) U-830, manufactured by Nidong Kabushiki Kaisha ]
I2959: 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one [ IRGACURE (registered trademark) 2959, manufactured by BASF ジャパン ]
MEK: methyl ethyl ketone
PGME: propylene glycol monomethyl ether
MeOH: methanol
Production example 1 production of perfluoropolyether (SM 1) having 4 acryloyl groups at each end via urethane bond
Into the threaded tube were charged 1.19g (0.5 mmol) of PFPE, 0.52g (2.0 mmol) of BEI, 0.017g of DOTDD (0.01 times the total mass of PFPE1 and BEI), and MEK1.67g. The mixture was stirred at room temperature (about 23 ℃) for 24 hours using a stirrer, to obtain a 50 mass% MEK solution of the objective compound SM 1.
Weight average molecular weight of obtained SM1 measured in terms of polystyrene by GPC: mw 3,000, dispersity: mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.
Production example 2 production of perfluoropolyether (SM 2) having 2 acryloyl groups at one of both ends and 4 acryloyl groups at the other of both ends via urethane bonds
To the threaded pipe were charged 1.19g (0.5 mmol) of PFPE, 0.36g (1.5 mmol) of BEI, 0.015g of DOTDD (0.01 times the total mass of PFPE1 and BEI), and MEK1.56g. The mixture was stirred at room temperature (about 23 ℃) for 72 hours using a stirrer, to obtain a 50 mass% MEK solution of the objective compound SM 2.
Weight average molecular weight of obtained SM2 measured in terms of polystyrene by GPC: mw of 2,750, dispersity: mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.
Production example 3 production of perfluoropolyether (SM 3) having 3 acryloyl groups at one end of both ends and 4 acryloyl groups at the other end of both ends via urethane bond
1.19g (0.5 mmol) of PFPE, 0.36g (1.5 mmol) of BEI, 0.07g (0.5 mmol) of AOI, 0.016g of DOTDD (0.01-fold of the total mass of PFPE1, BEI and AOI), and MEK1.64g were charged into the threaded pipe. The mixture was stirred at room temperature (about 23 ℃) for 72 hours using a stirrer, to obtain a 50 mass% MEK solution of the objective compound SM 3.
Weight average molecular weight of obtained SM3 measured in terms of polystyrene by GPC: mw of 2,900, dispersity: mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.
Examples 1 to 9 and comparative examples 1 to 8
The following components (1) to (4) were mixed to prepare a curable composition having a solid content concentration shown in table 1. Here, the solid component means a component other than the solvent. In table 1, [ parts ] represents [ parts by mass ], EO represents an oxyethylene group, and PO represents an oxy group (methylethylene group).
(1) A polyfunctional monomer: 100 parts by mass of a polyfunctional monomer shown in Table 1
(2) Surface modifier: surface modifier shown in Table 1 the amounts shown in Table 1 (in terms of solid content)
(3) Polymerization initiator: i2959 3 parts by mass
(4) Solvent: amounts reported in PGME Table 1
A4-size PET film (ルミラー (registered trademark) U403, manufactured by Toray corporation, thickness 100 μm) was easily adhered to both surfaces thereof]The curable composition was applied by a bar coater to obtain a coating film. The coating film was dried in an oven at 120 ℃ for 3 minutes to remove the solvent. The obtained film was irradiated under nitrogen atmosphere with an exposure of 300mJ/cm 2 The UV light of (2) was exposed to light, thereby producing a hard coat film having a hard coat layer (cured film) with a thickness of about 5 μm.
The hard coat films obtained were evaluated for scratch resistance (appearance, antifouling property), flex resistance and stretchability. The order of each evaluation is as follows. The results are shown in Table 2.
[ scratch resistance: appearance (C)
Stainless steel wool (ボンスター casing ボンスター (registered trademark) #0000 (super fine) manufactured by strain K.K.) mounted and reciprocating abrasion tester]Application of 250g/cm 2 The hard coat surface was wiped back and forth for 2,000 times under the load of (1), and the degree of damage was visually checked and evaluated according to the following criteria A, B and C. In addition, assuming practical use as a hard coat layer, at least B, preferably a, is required.
A: has no damage
B: with a part having a lesion
C: with damage to the whole surface
[ scratch resistance: antifouling property)
The water contact angle of the hard coat layer surface was measured before and after the abrasion resistance test, and the difference between the contact angle value before the test and the contact angle value before and after the test (contact angle before the test — contact angle after the test) was evaluated based on the following criteria a and C. In addition, the contact angle was determined by attaching 1 μ L of water to the surface of the hard coat layer, and measuring the contact angle θ at 5 seconds after that, and the average value thereof was taken as the contact angle value. In addition, a is preferable in the case of assuming practical use as a hard coat layer.
A: the contact angle value before the test is 90 degrees or more and the difference between the contact angle values before and after the test is less than 10 degrees
C: the contact angle value before the test is 90 degrees or more and the difference between the contact angle values before and after the test is 10 degrees or more, or the contact angle value before the test is less than 90 degrees
[ bending resistance ]
The hard coat film was cut into a rectangular shape having a length of 80mm and a width of 20mm to prepare a test piece. In the tester with the ejector pins, the short side of the test piece was fixed, and the test piece was bent 180 degrees with the hard coat layer outside for 1 to 2 seconds. The hard coat layer after bending was visually observed to confirm whether or not cracks were present. The mandrel was tested with a curvature radius of 1mmR, 2mmR, 3mmR, 5mmR, or 10mmR, and the minimum curvature radius at which no crack occurred was evaluated as the bending resistance according to the following criteria A, B and C. In addition, assuming practical use as a hard coat layer, at least B, preferably a, is required.
A: less than 3mmR
B:3mmR or more and less than 10mmR
C:10mmR or more
[ stretchability ]
The hard coat film was cut into a rectangular shape having a length of 60mm and a width of 10mm to prepare a test piece. The test piece was mounted on a jig of a universal testing machine so as to sandwich 20mm between both ends in the longitudinal direction thereof, and tensile tests were performed so that the elongation (= (increase in distance between jigs) ÷ (distance between jigs) × 100) became 2.5%, 7.5%, 10%. The hard coat layer of the test piece was visually observed, and the maximum elongation without generating cracks was evaluated as the stretchability according to the following criteria A, B and C. In addition, assuming practical use as a hard coat layer, at least B, preferably a, is required.
A: over 10 percent
B: more than 2.5 percent and less than 10 percent
C: less than 2.5 percent
[ Table 1]
TABLE 1
[ Table 2]
TABLE 2
As shown in tables 1 and 2, the hardcoats (examples 1 to 7) produced using the curable composition in which the oxyethylene-modified acrylate having 3 or more functional groups per 1mol of functional oxyethylene group was compounded as a polyfunctional monomer and perfluoropolyether SM1 having 4 acryloyl groups at both ends via urethane bonds was compounded as a surface modifier were excellent in scratch resistance and had bending resistance and appropriate stretchability. The hard coat films (examples 8 and 9) produced using the curable compositions containing perfluoropolyether SM2 or SM3 as a surface modifier in place of SM1 were excellent in scratch resistance and had bending resistance and appropriate stretchability.
On the other hand, hard coat films using 3-to 6-functional acrylates that are not modified with oxyethylene groups as polyfunctional monomers (comparative examples 1 to 4) are very poor in bending resistance and stretchability. In addition, the hard coating films of 3-functional acrylate modified with an oxy (methylethylene) group (comparative examples 5 and 6) had poor scratch resistance even when 1mol of oxyalkylene group was used per 1mol of functional group. Further, the hard coat film (comparative example 7) using an oxyethylene-modified acrylate and an acrylate having 3mol of oxyethylene groups per 1mol of the functional groups was inferior in antifouling property. The hard coat film (comparative example 8) containing no perfluoropolyether as a surface modifier was inferior in both scratch resistance and stain resistance.
Examples 10 to 12 and comparative example 9
The following components (1) to (4) were mixed to prepare a curable composition having a solid content concentration shown in table 3. Here, the solid content is a component other than the resin solvent. In table 3, [ parts ] represents [ parts by mass ], and EO represents an oxyethylene group.
(1) A polyfunctional monomer: 100 parts by mass of a polyfunctional monomer shown in Table 3
(2) Surface modifier: 0.2 part by mass (in terms of solid content) of the surface modifier shown in Table 3
(3) Polymerization initiator: i2959 3 parts by mass
(4) Solvent: meOH amounts reported in Table 3
A4-size PET film (ルミラー (registered trademark) U403, made by Toray corporation, 100 μm thick) having both surfaces easy to be bonded]The curable composition was applied by a bar coater to obtain a coating film. The coating film was dried in an oven at 65 ℃ for 3 minutes to remove the solvent. Irradiating the obtained film with an exposure of 300mJ/cm in a nitrogen atmosphere 2 The UV light (2) was exposed to light to form a hard coat film having a hard coat layer (cured film) with a thickness of about 5 μm.
The obtained hard coat film was evaluated for the aforementioned [ scratch resistance ], [ bendability ], and [ stretchability ], and also for wear resistance. The order of the wear resistance evaluation is as follows. The results are shown in Table 4.
[ wear resistance ]
The RUBBER was subjected to a reciprocating abrasion tester using a cylindrical RUBBER [ RUBBER STICK manufactured by Minoan Ltd. ],
]The hard coat surface was repeatedly wiped 3,000 times with a load of 1 kg. After 1. Mu.L of water was adhered to the wiped portion, the contact angle θ at 5 points was measured 5 seconds later, and the average value was evaluated as the contact angle value according to the following criteria A, B and C. In addition, assuming practical use as a hard coat layer, at least B, preferably a, is required.
A：θ≧80°
B：70°≦θ＜80°
C：θ＜70°
[ Table 3]
TABLE 3
[ Table 4]
TABLE 4
As shown in tables 3 and 4, the hard coat films (examples 10 to 12) produced using the oxyethylene-modified acrylate in which the number of functional groups is 3 or more and 1mol of oxyethylene groups per 1mol of functional groups is blended as the polyfunctional monomer and the curable composition in which perfluoropolyether SM1, SM2, or SM3 is blended as the surface modifier have excellent scratch resistance, bending resistance, and stretchability and have good abrasion resistance.
On the other hand, the hard coating film (comparative example 9) containing no perfluoropolyether as the surface modifier was poor in abrasion resistance.
Claims (9)
1. A curable composition comprising 100 parts by mass of an oxyethylene-modified polyfunctional monomer, 0.1 to 10 parts by mass of b perfluoropolyether, and 1 to 20 parts by mass of c a polymerization initiator that generates radicals by active energy rays,
the a oxyethylene group-modified polyfunctional monomer has at least 3 active energy ray-polymerizable groups and has an average oxyethylene group modification amount of less than 3mol per 1mol of the polymerizable groups,
the b perfluoropolyether has active energy ray-polymerizable groups via urethane bonds at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group, but the b perfluoropolyether does not include a perfluoropolyether having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bonds,
the b perfluoropolyether is:
a perfluoropolyether having a structural moiety represented by the following formula [1] and having 4 acryloyl groups at each of the two ends via the urethane bond,
a perfluoropolyether having a structural moiety represented by the following formula [1] and having 2 acryloyl groups at one end of the both terminals and 4 acryloyl groups at the other end of the both terminals via the urethane bond, or
A perfluoropolyether having a structural moiety represented by the following formula [1] and having 3 acryloyl groups at one end of the both terminals and 4 acryloyl groups at the other end of the both terminals via the urethane bond,
formula [1]In which n represents a repeating unit- [ OCF ] 2 CF 2 ]The number and repeating units of- [ OCF ] 2 ]-and n is from 5 to 30,
the a oxyethylene-modified polyfunctional monomer contains at least 1 monomer selected from the group consisting of an oxyethylene-modified polyfunctional (meth) acrylate compound and an oxyethylene-modified polyfunctional urethane (meth) acrylate compound.
2. The curable composition according to claim 1, wherein the average oxyethylene modification amount of the oxyethylene-modified polyfunctional monomer is 2mol or less based on 1mol of the polymerizable group.
3. The curable composition according to claim 1 or 2, further comprising a d solvent.
4. A cured film obtained from the curable composition according to any one of claims 1 to 3.
5. A hard coat film comprising a hard coat layer formed on at least one surface of a film substrate, the hard coat layer being the cured film according to claim 4.
6. A hardcoat film having a hardcoat layer on at least one surface of a film substrate, the hardcoat layer being formed by a method comprising: a step of forming a coating film by applying the curable composition according to any one of claims 1 to 3 on a film substrate, and a step of curing the coating film by irradiating the coating film with an active energy ray.
7. The hard coating film according to claim 5 or 6, wherein the film thickness of the hard coating layer is 1 to 10 μm.
8. A method for manufacturing a laminate, comprising: a step of forming a coating film by applying the curable composition according to any one of claims 1 to 3 on a film substrate, and a step of curing the coating film by irradiating the coating film with an active energy ray.
9. The curable composition according to claim 1 or 2, wherein the alpha oxyethylene-modified polyfunctional monomer is ethylene oxide-modified diglycerol tetraacrylate.
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| JP2018-128244 | 2018-07-05 | ||
| JP2018128244 | 2018-07-05 | ||
| PCT/JP2019/024994 WO2020008937A1 (en) | 2018-07-05 | 2019-06-24 | Curable composition for flexible coating |
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| CN112368305B true CN112368305B (en) | 2023-03-28 |
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| WO2020162332A1 (en) * | 2019-02-06 | 2020-08-13 | 日産化学株式会社 | Curable composition for anti-glare flexible hard coats |
| WO2020162326A1 (en) * | 2019-02-06 | 2020-08-13 | 日産化学株式会社 | Curable composition for flexible hard coat |
| KR102593819B1 (en) * | 2019-02-06 | 2023-10-25 | 닛산 가가쿠 가부시키가이샤 | Curable composition for anti-glare hard coat |
| WO2020162324A1 (en) * | 2019-02-06 | 2020-08-13 | 日産化学株式会社 | Curable composition for antistatic hard coating |
| WO2020162329A1 (en) * | 2019-02-06 | 2020-08-13 | 日産化学株式会社 | Curable composition for hard coating |
| CN113423513B (en) * | 2019-02-06 | 2023-08-15 | 日产化学株式会社 | Light-resistant hard coating curable composition |
| JP7074825B1 (en) | 2020-11-16 | 2022-05-24 | 株式会社ダイセル | Laminated film and foldable device |
| JP7031785B1 (en) | 2020-12-11 | 2022-03-08 | 東亞合成株式会社 | Composition for active energy ray-curable antiviral |
| JP2022093249A (en) * | 2020-12-11 | 2022-06-23 | 東亞合成株式会社 | Active energy ray-curable antiviral composition |
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| KR20230093369A (en) | 2023-06-27 |
| TWI791863B (en) | 2023-02-11 |
| JP2022164666A (en) | 2022-10-27 |
| JPWO2020008937A1 (en) | 2021-08-05 |
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| TW202016211A (en) | 2020-05-01 |
| JP7397412B2 (en) | 2023-12-13 |
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